Vulcanization



'0a. 2 6, 194s. R BASCOM 2,452,347

vVULCANI ZATION Original FiledMay l, 1957 Patented Oct. 26, 1948 VULCANIZATION Roger Charles Bascom, Port Clinton, Ohio, as-

signer to Rubatex Products, Inc., New York, N. Y., a corporation of Delaware Original application May 1, 1937, Serialr No. 140,156. Divided and this application February 13, 1943, Serial No. 475,800

1 Claim. (Cl. 260-725) This case is a division of my application Serial No. 140,156, led May 1, 1937, now Patent No. 2,310,926.

My invention relates to a novel process for manufacturing rubber and more particularly relates to a novel process for manufacturing expanded rubber both of the cell tight cellular type and of the sponge or inter-connecting cellular type.

In the manufacture of expanded rubber, it is essential that vulcanization should synchronize with the gassing of the rubber and, particularly, that no or very slight vulcanization should occur before the rubber has been at least gassed.

Usually the accelerators which are employed tend to cause vulcanization to occur at some stage in the process before the time when it is desired that Vulcanization should begin, i. e., before gassing, and in this manner, produces a defect in the final product.

Moreover, not only must vulcanization occur at the proper stage, the degree of vulcanization is important since it must be just sufficient to hold the gas and not so much that it creates any undue strain in expanding the rubber.

This problem is accentuated by the fact that in gassing rubber, particularly when the gas is applied externally under pressure, the degree of penetration and absorption depends upon the plasticized condition of the rubber. The plasticity of the rubber, in turn, is a function of the temperature. In practice I have found that the l, optimum penetration'and absorption of nitrogen gas at the normal pressures employed, i. e., 3000 pounds per square inch is obtained at 265 Fahrenheit. In fact, from experimentation, I have found that saturation of rubber one-half inch thick will take four hours when the rubber is plasticized at a temperature of 215 Fahrenheit and the pressure applied is 3000 pounds per square inch. At a temperature of 300 Fahrenheit, the same thickness of rubber will be saturated in one hour using the same pressure. At this high temperature, however, accelerators will vulcanize the rubber so that with the use of high tempera- 2 ture it is impractical, if not inoperative, to employ accelerators.

I have discovered a process in which I eliminate the presence of accelerators during the period of penetration or absorption of the gas in the rubber, the rubber having as a constituent a retarder to prevent substantially any Vulcanization even at the temperature of 300 F. at which even rubbersulphur mixes tend to vulcanize. A gaseous accelerator is introduced after gassing has been either partially or substantially completed in order to control the vulcanization to that stage.

Accordingly, an object of my invention is to provide a novel process for the manufacture of rubber.

A further object of my invention is to provide a novel process for manufacturing gas-expanded rubber. y

Still another object of my invention is to provide a novel process for critically controlling the period when vulcanization starts in the manufacture of rubber.

Still another object of my invention is the step in the manufacture of expanded rubber of introducing ammonia gas after the rubber has been either partly or completely gassed.

It is well known in the art that aldehydes, such as formaldehyde, acetaldehyde, 'furfuraldehyda glucose, and benzaldehyde, are retarders of vulcanization. Accordingly, in carrying out my invention I have found that I may by the addition ofk such retarding agents prevent Vulcanization even at the higher temperatures most desirable for plasticizing the rubber and by using ammonia gas convert these retarding agents themselves into accelerators. This is due to the fact that ammonia gas combines with these aldehydes to form aldehyde-ammonia condensation products. A1- dehyde-ammonia condensation products have long been known as good accelerators for vulcanization. Thus, for example, hexamethylene tetra-amine is a good example of an accelerator which is a condensation product of formaldehyde and ammonia gas. Similarly, acetaldehyde-ammonia is a condensation product of acetaldehyde ber to the desired temperature. 4fwell known in the art for this purpose, an inert and ammonia. By employing the retarders re ferred to above and admitting ammonia gas at the proper stage in the process, I convert these retarders to accelerators, thus eiectively controlling the degree of vulcanization until the proper stage and thereafter obtaining a high-speed vuloanization. This control is particularly important in the manufacture of expanded rubber where it is desired during the early stages of the process to work With a rubber composition which is extremely plastic and control the composition so that during the gassing stage, the rubber vulcanizes so that its physical state changes to a slightly less plastic state.

Accordingly, an object of my invention is to provide a novel process inthe manufacture of rubber which 'comprises normally employing retarders during the early stages of the process and converting these into accelerators in the subsequent stages.

A further object of my invention is to provide a novel process for controlling acceleration in the manufacture of rubber.

Still a further object of my invention is to provide a process in which aldehydes are converted into aldehyde-ammonia condensation products.

There are other objects of 'my invention which, together with the foregoing, will appear in the detailed description which is to follow.

Figure 1 is a side elevation and cross-section of the` apparatus showing the means by which the process of this invention nay be carried out.

Referring more. specifically to the drawing, in

v Figure l 'sfsh'ov'vria chamber I which a truck 2 containing rubber 3 is placed. By means of a pump 4 agas is orcd'into'the chamber l to impregnate the vrubber through the opening 5. The pressure ofthe gas is controlled by means of the .gauge 6 and the valve V'L The chamber is heated byheatingpipe. B supplied with heating fluid in the pipe S- A steam trap I ll provides for the out- 'flow of the heating fluid. A door Il is provided 4at the side of the chamber so that the truck may beinse'r'ted and Withdrawn. Through a gas pipe I3 and 'a nozzle i4, the gas which accelerates the vulcanization is brought into the chamber. The 'flow of this gas is' controlled by the 'valve l5.

When carrying out my invention I employ any lone of theiormulas mentioned herewith and proceed vas dscribedbelow.

After suitable mixing andcalendering of these compounds in a, manner well'k'nown inthe art I prepare therubber for gassing` by admitting it to an autoclave y'and raisingits temperature to from 215 to 300" and preferably to 300 F. At these temperatures as already explained the normal tendency for the rubber to vulcanize is inhibited bythe retarder employed.

This tempera-ture rise may be obtained either by directly heating the rubber or in a preferred form by introducing hot gas with which the rubber is. to be saturated s'uiiicient to bring the rub- As is already gas, such as nitrogen is employed atr a pressure ofthe order of 3000 pounds per square inch, although it lWill be understood that this pressure may be varied in accordance with the desired density of product. Atthe high temperature at which the rubber is'main'tained, it is relatively plastic so thatthefgas `easily penetrates `and is absorbed by the rubber.

In order to understand the importance of this plasticizini:T itl should be understood that in subj-ectin'gthe rubber to gas at this pressure some of thegas goes into solution in the rubber forming a homogeneous mixture of gas and rubber, the dissolved gas being dispersed throughout in particles which are of the order of molecular size. Solutions of gas and rubber are a physical phenomenon characterized by an appreciable time for equilibrium to occur, that is, there is a measurable time necessary before the solution becomes homogeneous throughout the mass of rubber. Solution naturally occurs on the surface first and disperses toward the center thereafter. This dispersion is referred to as penetration or impregnation. l

The speed of penetration is the velocity at which this dispersion occurs. When the rubber solution is substantially homogeneous, complete penetration has been obtained. Saturation of the rubber bygas occurs when the maximum amount of gas which the rubber can hold is in solution. This saturation, in turn, will vary with temperature and pressure of the gas.

It will be clear from the above that by raising the rubber temperature to from 215 to 300 F., the rate of penetration will be increased so that the rubber one-half inch thick is saturated With gas in about an hour at 300 F.

The gas pressure is now released and the rubber is permitted to expand. In expanding bubbles of gas are formed throughout the rubber mass, each bubble producing minute cells. These cells may be individually sealed cells or they may be inter-communicating cells, depending on the state of vulcanization, therate of pressure release and other factors not well known to date.

After the Ynitrogen pressure has beenv removed, ammoniak gas is admitted to the rubber at a pressure of the order of 10 pounds persquare inch above atmospheric pressurev andat approximately the temperature of the rubber andthis pressure is maintained until complete vulcanization occurs. The ammonia gas neutralizes the retarder and at the same time acts as an accelerator to initite and assist in the completion of vulcanization.`

Although in the above, I have describedA the processas being carried on entirely in an autoclave, it is also possible in accordance'with my invention to remove. the rubber -fromithe expensive autoclave whichnecessarily if it is to maintainpressures ofA the order of 3000 pounds vper square inch is a relatively expensive device and carry on the vulcanization by employing a large and less expensveautoclave into which the aminonia gas is admitted in carrying out the above process.

It Will be noted that penetration of the gassed and expanded rubber by ammonia is very rapid.

Full penetration at room temperature is accomplished in less than one hour f or samples one inch thick or more after expansion.

In another form of my invention'I mayrnix my ammonia gas with'my nitrogen admitting the two to the rubber and thoroughly saturating the rubber with both the'nitrogen and the ammonia gas simultancouslyand at a combined pressure of 3000 poundsper square inch. The ammonia in that case will institute a` partial vulcanization during gassing. In this mo'diiied form of the process, full advantage of the plasiicizing temperature cannot be taken because of the tendency of ammonia to cause vulcanizati'o'n and the plasticizingtemperatures must be kept inthe Vorder of 215 F. to prevent complete yulc'anization during gassing. On the other hand, the ammonia adds its blowing eiTect to the nitrogen. A-'iter gassing, complete vulcanization is obtained byraising therubber temperature and then releasing the pressure,

Soft Hard Rubber o 10o Sulphur 3 50 Zinc Oxide 5 Salcylic Acid 2 2 Condensation products of Methylene and Aniline l Rubber 100 100 Sulphur 3 50 Zinc Oxide 5 Paraformaldchyde 1 1 Hard reinforced Rubber 100 Sulphur 50 Phenol-Formaldehyde Type B. Resin 50 Rubber Sulphur Zinc Oxid Condensa aniline Paraiormaldehyde In each of the compounds employed, the reactions which take place when the ammonia gas is admitted for transforming the retarder into an accelerator may be explained as follows:

In the case of the formula No. 1 where no retarder is employed and no accelerator; substantially no vulcanization occurs until the ammonia gas is admitted, even though the temperature of the rubber reaches a temperature on the order of 260 F. Accordingly, all the necessary action during the gassing operation may be carried out without in any way endangering the process by too much vulcanization. At the proper stage in the operations the admission of the ammonia gas is, in eiiect, an introduction of an accelerator which will instigate vulcanization and which will then continue in accordance with my process.

In the case of formula No. 2 employing a retarder, salicylic acid, and an accelerator which is the condensation product of methylene and aniline, the salicylic acid retards the vulcanization suciently so there is substantially no vulcanization during the gassing operation. Accordingly, plasticizing temperatures as high as 300 F. may be employed. During the subsequent treatment with ammonia gas, the salicylic acid is neutralized and the accelerator in conjunction with ammonia which is also an accelerator, causes the rubber to vulcanize in a reasonably short time.

In the third case, formula No. 3, I have used paraformaldehyde as an example. Paraformaldehyde acts as a retarding agent, electively retarding the vulcanization during the gassing stage. Here again a plasticizing temperature of 300 F. is practical. However, during the treatment with ammonia gas, paraformaldehyde and ammonia condense to form hexamethylene tetraamine which is an eiiective accelerator of rubber vulcanization.

In the fourth case, formula No. 4, for reinforced hard material contains rubber, sulphur and a phenolformaldehyde resin, condensation of which has been carried to the B stage where the resin is still fusible and still solublei This par-l ticular resin that I am using has a surplus of formaldehyde incorporated with it and required ammonia as a'catalyst to complete the condensation to a marketable product. It is obvious that the surplus formaldehyde in the resin will act, as far as the rubber mix goes, similar -to compound No. 3, preventing vulcanization in the gassing operation but being converted to an accelerator', hexamethylene tetra-amine, during the treatment with ammonia gas.

In the manufacture of hard expanded rubber, it is desirable to use carbon dioxide as the gassing agent because of its extreme solubility compared to nitrogen in rubber. By using phenol-formaldehyde resin we can reinforce the cell structure of our hard material sufficiently to withstand the partial vacuum in the cells which occurs when the carbon dioxide diffuses through the A cells into the atmosphere.

As a further variation in my process, using the compound No. 5 which contains the condensation product of acetaldehyde and aniline as an ac- ,r celerator and paraformaldehyde as a retarder,

the gassing operation is conducted in the same Way as the others. However, since paraformal-v dehyde will condense with ammonia gas to form hexamethylene tetra-amine, the combination of hexamethylene and the condensation product of acetaldehyde and aniline will cause vulcanization to ensue at very 10W temperatures of the order of F.

It will be noted that in the case of hard materials, the proportion of sulphur being higher than in the case of soft, it is necessary to use either less accelerator or more retarder to achieve results comparable with the soft.

The methods I propose to employ for the vulcanization of our finished material are obvious from the above description, but there will be, of course, variations of the above procedure, depending upon the finished product desired. For example, it will be possible to gas the rubber with any of the above compounds and subsequently treat the expanded vulcanized or partially vulcanized rubber with ammonia gas at room temperature. Thereafter, I may place the rubber in molds and complete the vulcanization between steam platens. Likewise the above compounds may be modied with iilters, reclaimed rubber or other well known compounding ingredients.

From the above, it will now be clear that I have discovered a process for the manufacture of rubber in which vulcanization is controlled as desired during a predetermined stage in the manufacture, notwithstanding the fact that the vulcanizing agent sulphur is a part of the ingredients during this stage. I have more specically illustrated this principle as applied to the manufacture of gas expanded rubber where it is particularly important that during the gassing operation there shall be substantially no vulcanization. As illustrated in these examples, I have accomplished this in one form of my invention by omitting accelerators during the gassing operation or by the use of retarders which act in a positive manner to control closely any such vulcanization. After the gassing is completed, I admit ammonia which either chemically transforms the retarder or acts in conjunction with the accelerators already present to instigate and accelerate vulcanization.

However, that same principle may Ibe carried out by other compositions than ammonia gas. Thus, for example, I may replace the ammonia gas with a compound such as sulphur chloride.

Infthat,"case,v however,`- .myoriginarrubber com positionlfdoes Ynot `.contain any` l or substantially any sulphur. After the A gassing; operation has been4 completed; I admit sulphur chloridei as :a gaseous vapor at ,reunir-temperatures.; It Will be understood, however, thatduringthe :gassingeom eratons thesame conditions obtainedfasdescribed above,l that is; the .rubber .was plasticized to .temperatur-es ,of the order off-.280 F. and inctachv if desired, can go :muchY higher. since Atherez-is` .very little sulphur present. 'I'hevfsulphurchloride acts as aevulcanizingagent flike sulphurrexceptfthat it dqes :not-require' any accelerator to carry. on rapid Yulcanizationf..

In-thethird process I may;-use hydrogen' -su1- phide-and sulphurV dioxidefvrhiclfiy are :alternately permitted .to.penetrate` tlfie-egassed rubber atvfthe completion of the-gassing operationi In this'case alsoit will be understoodl that Vvery littleonno sulphur need be mixed withy thefrubber,v compound' during the -gassing operations;y

Thus rit/Will: be Aseen lthat Iam" not limitedto the use of ammoniaior preventing acceleration in the :manufacture of gasy expandedrubber dur-Y 8 given-,.but-only insofar as sei; forth-.incthefappended claim..

I claim:

The method. of manufacturing gas expanded rubber which comprises forming a rubber mix free from any vulcanizing agent heating the rubber mix to a temperature of the order of 280 F., gassing the rubber mix at a pressure of the orderr of 3000 ypounds per square inch to expandthe same fully to its iinal shape; thereafter reducing the gas pressure and adding a Vulcanizing agent including sulphur compounds to the expanded rubber and Vulcanizing the rubber.

ROGER CHARLESfBASCOM-.l

REFERENCES CITED The following references are of record -irrthe le of this patent:

UNITED STATES PATENTS Number Name Date 1,089,482 Laarmann Mar. 10, 1914 1,487,880 Peaohey Mar. 25, 1924 1,630,721 Snelling May 31,l 1927 1,717,168 Near June 11, 1929 2,067,020 Roberts Jan. 5, 1937 2,158,083 Peel May 16, 1939 2,231,950 Roberts et al Feb. 18,y 194:1 2,310,926 Bascom Feb. 1651943 

